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1.
Water Res ; 258: 121811, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38833811

ABSTRACT

Urban stormwater runoff is considered a key component of future water supply portfolios for water-stressed cities. Beneficial use of runoff, such as capture for recharge of drinking water aquifers, relies on improved stormwater treatment. Many dissolved constituents, including metals and trace organic contaminants (TrOCs) such as hydrophilic pesticides and poly- and perfluoroalkyl substances (PFASs), are of concern due to their toxicity, persistence, prevalence in stormwater runoff, and poor removal in conventional stormwater control measures. This study explores the operational flow rate limitations of black carbon (BC)-amended engineered media filters for removal of a wide suite of dissolved metals and TrOCs and provides validation for a previously developed predictive TrOC transport model. Column experiments were conducted with face velocities of 40 and 60 cm h-1 to assess Douglas Fir-based biochar and regenerated activated carbon (RAC) filter performance in light of media-contaminant removal kinetic limitations. This study found that increasing the face velocity in BC-amended filters to 40 and 60 cm h-1, which are representative of field conditions, decreased the removal of total suspended solids, turbidity, dissolved hydrophilic TrOCs, and PFASs when expressed as volume treated relative to previous studies conducted at 20 cm h-1. Dissolved metals and hydrophobic TrOCs removal were not substantially affected by the increased flow rates. A predictive 1-d intraparticle pore diffusion-limited sorption model with sorption and effective tortuosity parameters determined previously from experiments conducted at 20 cm h-1 was validated for these higher flow rates. This work provides insights to the kinetic limitations of contaminant removal within biochar and RAC filters and implications for stormwater filter design and operation.


Subject(s)
Filtration , Water Pollutants, Chemical , Water Purification , Water Pollutants, Chemical/chemistry , Kinetics , Water Purification/methods , Charcoal/chemistry , Rain , Soot/chemistry , Carbon/chemistry
2.
Environ Sci Technol ; 58(9): 4046-4055, 2024 Mar 05.
Article in English | MEDLINE | ID: mdl-38390867

ABSTRACT

In California, recent Bay-Delta Plan legislation attempts to balance water supply and ecosystem protection by requiring 40% of the flow to remain in-stream in the Tuolumne River from February through June. Serious questions remain about what this means for the Bay Area water supply, especially during drought. Our work develops a new approach to analyze how in-stream flow policy coupled with climate change could impact regional water supply over the coming decades. Results show that the new in-stream flow demand would exceed urban water deliveries in a typical year. In wet years, water supply performance is minimally impacted, but in drought, the policy can lead to less water in storage, delayed reservoir recovery, and increased time at critically low storage. Storage impact exceeding 50 000 acre-feet (60 million m3) is anticipated with at least 18% frequency, demonstrating that, climate uncertainty notwithstanding, this impact must be planned for and managed to ensure a reliable future water supply.


Subject(s)
Droughts , Ecosystem , Water Supply , Rivers , Water
3.
Environ Sci Technol ; 57(38): 14417-14428, 2023 09 26.
Article in English | MEDLINE | ID: mdl-37699564

ABSTRACT

Improved stormwater treatment is needed to prevent toxic and mobile contaminant transport into receiving waters and allow beneficial use of stormwater runoff. In particular, safe capture of stormwater runoff to augment drinking water supplies is contingent upon removing dissolved trace organic contaminants (TrOCs) not captured by conventional stormwater control measures. This study builds upon a prior laboratory-based column study investigating biochar and regenerated activated carbon (RAC) amendment for removing hydrophilic trace organic contaminants (HiTrOCs) and poly- and perfluoroalkyl substances (PFASs) from stormwater runoff. A robust contaminant transport model framework incorporating time-dependent flow and influent concentration is developed and validated to predict HiTrOC and PFAS transport in biochar- and RAC-amended stormwater filters. Specifically, parameters fit using a sorption-retarded intraparticle pore diffusion transport model were validated using data further along the depth of the column and compared to equilibrium batch isotherms. The transport model and fitted parameters were then used to estimate the lifetime of a hypothetical stormwater filter in Seal Beach, CA, to be 35 ± 6 years for biochar- and 51 ± 17 years for RAC-amended filters, under ideal conditions with no filter clogging. This work offers insights on the kinetics of HiTrOC and PFAS transport within biochar and RAC filters and on the impact of filter design on contaminant removal performance and longevity.


Subject(s)
Caniformia , Fluorocarbons , Seals, Earless , Water Purification , Animals , Rain , Water Supply , Soot
4.
ACS Environ Au ; 3(1): 34-46, 2023 Jan 18.
Article in English | MEDLINE | ID: mdl-36691657

ABSTRACT

Urban stormwater runoff is a significant driver of surface water quality impairment. Recently, attention has been drawn to potential beneficial use of urban stormwater runoff, including augmenting drinking water supply in water-stressed areas. However, beneficial use relies on improved treatment of stormwater runoff to remove mobile dissolved metals and trace organic contaminants (TrOCs). This study assesses six engineered media mixtures consisting of sand, zeolite, high-temperature gasification biochar, and regenerated activated carbon (RAC) for removing a suite of co-contaminants comprising five metals, three herbicides, four pesticides, a corrosion inhibitor, six per- and polyfluoroalkyl substances (PFASs), five polychlorinated biphenyls (PCBs), and six polycyclic aromatic hydrocarbons (PAHs). This long-term laboratory-scale column study uses a novel approach to generate reproducible synthetic stormwater that incorporates catch basin material and straw-derived dissolved organic carbon. Higher flow conditions (20 cm hr-1), larger sized media (0.42-1.68 mm), and downflow configuration with outlet control increase the relevance of this study to better enable implementation in the field. Biochar- and RAC-amended engineered media filters removed nearly all of the TrOCs in the effluent over the course of three months of continuous flow (480 empty bed volumes), while sample ports spaced at 25% and 50% along the column depth provide windows to observe contaminant transport. Biochar provided greater benefit to TrOC removal than RAC on a mass basis. This study used relatively high concentrations of contaminants and low biochar and RAC content to observe contaminant transport. Performance in the field is likely to be significantly better with higher biochar- and RAC-content filters and lower ambient stormwater contaminant concentrations. This study provides proof-of-concept for biochar- and RAC-amended engineered media filters operated at a flow rate of 20 cm hr-1 for removing dissolved TrOCs and metals and offers insights on the performance of biochar and RAC for improved stormwater treatment and field trials.

5.
ACS ES T Eng ; 3(1): 121-130, 2023 Jan 13.
Article in English | MEDLINE | ID: mdl-36660091

ABSTRACT

Anaerobic treatment of municipal wastewater with the staged anaerobic fluidized bed membrane bioreactor (SAF-MBR) shows promise to transform secondary wastewater treatment into an energy-positive process. However, the dissolved methane in SAF-MBR effluent needs to be recovered to reach net energy positive. To recover this methane for energy generation, an air stripping system was constructed downstream of a pilot-scale SAF-MBR facility and operated for over 80 days. The process removed 98% of effluent dissolved methane, and with the addition of intermittent disinfection recovered an average of 90% of the dissolved methane. The exit gas from air-stripping comprised 1.5-2.5% methane and could be utilized by blending with biogas produced from primary solids digestion and the SAF-MBR in an on-site combustion process. The direct energy costs for air stripping methane are <1% of the energy recoverable from the dissolved methane, not accounting for siloxane or sulfide scrubbing. Only siloxanes were observed at levels impacting combustion in this study, with 1.6 mg Si/m3 present in the blended biogas and air stripping mixture. The fate of a subset of trace organic contaminants was examined across the air stripping unit to check for aerobic degradation by methanotrophs or other opportunistic aerobes. Only 1,4-dioxane and benzotriazole showed statistically significant removal among 17 compounds screened, with 0.53 ± 0.13 and 0.34 ± 0.15 fraction removal, respectively. Our results indicate that air stripping is an energy efficient and robust technology for dissolved methane removal and onsite utilization for heat and electricity generation from anaerobic treatment of municipal wastewater.

6.
Water Res ; 226: 119246, 2022 Nov 01.
Article in English | MEDLINE | ID: mdl-36288663

ABSTRACT

Stormwater runoff capture and groundwater recharge can provide a sustainable means of augmenting the local water resources in water-stressed cities while simultaneously mitigating flood risk, provided that these processes do not compromise groundwater quality. We developed and tested for one year an innovative pilot-scale stormwater treatment train that employs cost-effective engineered geomedia in a continuous-flow unit-process system to remove contaminants from urban runoff during aquifer recharge. The system consisted of an iron-enhanced sand filter for phosphate removal, a woodchip bioreactor for nitrate removal coupled to an aeration step, and columns packed with different configurations of biochar- and manganese oxide-containing sand to remove trace metals and persistent, mobile, and toxic trace organic contaminants. During conditioning with authentic stormwater runoff over an extended period (8 months), the woodchip bioreactor removed 98% of the influent nitrate (9 g-N m-3 d-1), while phosphate broke through the iron-enhanced sand filter. During the challenge test (4 months), geomedia removed more than 80% of the mass of metals and trace organic compounds. Column hydraulic performance was stable during the entire study, and the weathered biochar and manganese oxide were effective at removing trace organic contaminants and metals, respectively. Under conditions likely encountered in the field, sustained nutrient removal is probable, but polar organic compounds such as 2,4-D could breakthrough after about a decade for conditions at the study site.


Subject(s)
Water Purification , Rain , Nitrates , Water Supply , Metals , Organic Chemicals , Organophosphates , Phosphates , Iron
7.
Environ Sci Technol ; 53(7): 3634-3644, 2019 04 02.
Article in English | MEDLINE | ID: mdl-30900451

ABSTRACT

Urban-use pesticides are of increasing concern as they are widely used and have been linked to toxicity of aquatic organisms. To assess the occurrence and treatment of these pesticides in stormwater runoff, an approach combining field sampling and watershed-scale modeling was employed. Stormwater samples were collected at four locations in the lower San Diego River watershed during a storm event and analyzed for fipronil, three of its degradation products, and eight pyrethroids. All 12 compounds were detected with frequency ranging from 50 to 100%. Field results indicate pesticide pollution is ubiquitous at levels above toxicity benchmarks and that runoff may be a major pollutant source to urban surface waters. A watershed-scale stormwater model was developed, calibrated using collected data, and evaluated for pesticide storm load and concentrations under several management scenarios. Modeling results show that enhanced stormwater control measures, such as biochar-amended biofilters, reduce both pesticide storm load and toxicity benchmark exceedances, while conventional biofilters reduce the storm load but provide minimal toxicity benchmark exceedance reduction. Consequently, biochar amendment has the potential to broadly improve water quality at the watershed scale, particularly when meeting concentration-based metrics such as toxicity benchmarks. This research motivates future work to demonstrate the reliability of full-scale enhanced stormwater control measures to treat pollutants of emerging concern.


Subject(s)
Pesticides , Water Pollutants, Chemical , Environmental Monitoring , Rain , Reproducibility of Results
8.
Environ Sci Technol ; 53(6): 3128-3139, 2019 03 19.
Article in English | MEDLINE | ID: mdl-30702865

ABSTRACT

To address water scarcity, cities are pursuing options for augmenting groundwater recharge with recycled water. Ozone-based treatment trains comprising ozone and biologically activated carbon potentially offer cost-effective alternatives to membrane-based treatment, the standard process for potable reuse in numerous countries. However, regulations in multiple states effectively limit the extent to which ozone-based treatment alone can produce recycled water for groundwater recharge. To investigate the trade-offs between treatment costs and regulatory constraints, this study presents methods for modeling and optimizing designs for (1) producing recycled water using membrane-based treatment, ozone-based treatment, and hybrid treatment trains comprising ozone-based treatment with a membrane sidestream, and (2) delivering that water to stormwater spreading basins. We present a case study of Los Angeles, CA, to demonstrate the model's application under realistic conditions, including regulations that limit spreading recycled water based on its concentration of total organic carbon and the extent of dilution. While the membrane-based treatment train exhibits economies of scale, we demonstrate how regulatory constraints create a diseconomies of scale effect for hybrid treatment systems because larger scales necessitate a higher proportion of recycled water undergo membrane treatment. Nevertheless, relative to membrane-based treatment, we identify opportunities for ozone-based or hybrid treatment trains to reduce treatment costs and energy use by up to 62% and 59%, respectively, for systems with up to 1 m3/s (23 million gallons per day) mean water recycling rate, potentially lowering the barrier for decentralized water recycling systems. This modeling approach could inform planning and policy regarding recycled water projects for groundwater recharge through spreading basins and, with additional modification, other potable reuse applications.


Subject(s)
Ozone , Water Pollutants, Chemical , Water Purification , Los Angeles , Water
9.
Water Res ; 154: 1-11, 2019 05 01.
Article in English | MEDLINE | ID: mdl-30763870

ABSTRACT

Stormwater is increasingly being valued as a freshwater resource in arid regions and can provide opportunities for beneficial reuse via aquifer recharge if adequate pollutant removal can be achieved. We envision a multi-unit operation approach to capture, treat, and recharge (CTR) stormwater using low energy, cost-effective technologies appropriate for larger magnitude, less frequent events. Herein, we tested nutrient, metal, and trace organic contaminant removal of a pilot-scale CTR system in the laboratory using biochar-amended woodchip bioreactors following eight months of aging under field conditions with exposure to real stormwater. Replicate columns with woodchips and biochar (33% by weight), woodchips and straw, or woodchips only were operated with continuous, saturated flow for eight months using water from a watershed that drained an urban area consisting of residential housing and parks in Sonoma, California. After aging, columns were challenged for five months by continuous exposure to synthetic stormwater amended with 50 µg L-1 of six trace organic contaminants (i.e., fipronil, diuron, 1H-benzotriazole, atrazine, 2,4-D, and TCEP) and five metals (Cd, Cu, Ni, Pb, Zn) frequently detected in stormwater in order to replicate the treatment unit operation of a CTR system. Throughout the eight-month aging and five-month challenge experiment, nitrate concentrations were below the detection limit after treatment (i.e., <0.05 mg N L-1). The removal efficiencies for metals in all treatments were >80% for Ni, Cu, Cd, and Pb. For Zn, about 50% removal occurred in the woodchip-biochar systems while the other systems achieved about 20% removal. No breakthrough of the trace organic compounds was observed in any biochar-containing columns. Woodchip columns without biochar removed approximately 99% of influent atrazine and 90% of influent fipronil, but exhibited relatively rapid breakthrough of TCEP, 2,4-D, 1H-benzotriazole, and diuron. The addition of straw to the woodchip columns provided no significant benefit compared to woodchips alone. Due to the lack of breakthrough of trace organics in the biochar-woodchip columns, we estimated column breakthrough with a diffusion-limited sorption model. Results of the model indicate breakthrough for the trace organics would occur between 10,000 and 32,000 pore volumes. Under ideal conditions this could be equivalent to decades of service, assuming failure by other processes (e.g., clogging, biofouling) does not occur. These results indicate that multiple contaminants can be removed in woodchip-biochar reactors employed in stormwater treatment systems with suitable flow control and that the removal of trace organic contaminants is enhanced significantly by addition of biochar.


Subject(s)
Bioreactors , Denitrification , California , Charcoal , Metals
10.
Environ Sci Technol ; 53(10): 5534-5542, 2019 05 21.
Article in English | MEDLINE | ID: mdl-30807122

ABSTRACT

The capture, treatment, and recharge of urban runoff can augment water supplies for water-scarce cities. This article describes trends in urban stormwater capture for potable water supply using examples from the U.S. and Australia. In water-limited climates, water supply potential exists for large scale stormwater harvesting and recharge, such as neighborhood-scale and larger projects. The beneficial use of urban stormwater to meet nonpotable water demands has been successfully demonstrated in the U.S. and internationally. However, in terms of potable water use in the U.S., the lack of a regulatory framework and uncertainty in treatment and water quality targets are barriers to wide-scale adoption of urban stormwater for recharge, which is not so evident in Australia. More data on urban stormwater quality, particularly with respect to pathogens and polar organic contaminants, are needed to better inform treatment requirements. New technologies hold promise for improved operation and treatment, but must be demonstrated in field trials. Stormwater treatment systems may be needed for large-scale recharge in highly urbanized areas where source control is challenging. The co-benefits of water supply, urban amenities, and pollution reduction are important for financing, public acceptance and implementation-but are rarely quantified.


Subject(s)
Rain , Water Supply , Australia , Cities , Water Movements , Water Quality
12.
Environ Sci Technol ; 52(11): 6370-6379, 2018 06 05.
Article in English | MEDLINE | ID: mdl-29676892

ABSTRACT

Stormwater best management practices (BMPs) are implemented to reduce microbial pollution in runoff, but their removal efficiencies differ. Enhanced BMPs, such as those with media amendments, can increase removal of fecal indicator bacteria (FIB) in runoff from 0.25-log10 to above 3-log10; however, their implications for watershed-scale management are poorly understood. In this work, a computational model was developed to simulate watershed-scale bacteria loading and BMP performance using the Ballona Creek Watershed (Los Angeles County, CA) as a case study. Over 1400 scenarios with varying BMP performance, percent watershed area treated, BMP treatment volume, and infiltrative capabilities were simulated. Incremental improvement of BMP performance by 0.25-log10, while keeping other scenario variables constant, reduces annual bacterial load at the outlet by a range of 0-29%. In addition, various simulated scenarios provide the same FIB load reduction; for example, 75% load reduction is achieved by diverting runoff from either 95% of the watershed area to 25 000 infiltrating BMPs with 0.5-log10 removal or 75% of the watershed area to 75 000 infiltrating BMPs with 1.5-log10 removal. Lastly, simulated infiltrating BMPs provide greater FIB reduction than noninfiltrating BMPs at the watershed scale. Results provide new insight on the trade-offs between BMP treatment volume, performance, and distribution.


Subject(s)
Waste Management , Water Purification , Bacterial Load , California , Rain
13.
Environ Toxicol Chem ; 37(7): 2013-2021, 2018 07.
Article in English | MEDLINE | ID: mdl-29521428

ABSTRACT

We evaluated bioturbation as a facilitator for in situ treatment with a thin layer of activated carbon to treat dichlorodiphenyltrichloroethane (DDT)-contaminated sediment and contaminant influx by sediment deposition. Using the freshwater worm Lumbriculus variegatus as a bioturbator, microcosm time-series studies were conducted for 4 mo and monitored for DDT flux and porewater concentration profiles by polyethylene passive samplers. With bioturbators present, the thin-layer activated carbon amendment reduced DDT flux by >90% compared with the same simulated scenario without activated carbon amendment. In contrast, a clean sediment cap without activated carbon was ineffective in reducing flux when bioturbation was present. In simulated scenarios with contaminant influx through deposition of contaminated sediment, bioturbation facilitated in situ activated carbon treatment, reducing 4-mo DDT flux by 77% compared with the same scenario without bioturbation. Porewater concentration profiles and activated carbon dose profiles confirmed effective mixing of activated carbon particles down to 1-cm depth. A mass transfer model was developed to predict flux with consideration of bioturbation and sediment deposition processes. Predicted flux values were consistent with experimental results and confirm that bioturbation activity helps reduce DDT sediment-to-water fluxes in activated carbon-treated sediment with recontamination by contaminated sediment deposition. To our knowledge, this is the first study to combine experimental and modeling results showing how bioturbation enhances activated carbon amendment effectiveness against ongoing contaminant influx by sediment deposition. Environ Toxicol Chem 2018;37:2013-2021. © 2018 SETAC.


Subject(s)
Charcoal/chemistry , DDT/isolation & purification , Geologic Sediments/chemistry , Animals , DDT/toxicity , Fresh Water , Models, Theoretical , Oligochaeta/drug effects , Polyethylene/chemistry , Time Factors , Water Pollutants, Chemical/toxicity
15.
Environ Pollut ; 231(Pt 2): 1380-1387, 2017 Dec.
Article in English | MEDLINE | ID: mdl-28943348

ABSTRACT

Sorbents amended to sediments in situ for sequestration of hydrophobic organic contaminants (HOCs) may be swept away from the treated sites due to hydrodynamic forces applied to the sediment surface. The purpose of this study is to examine the possibility of recovery of HOC availability in sorbent-amended sediment after complete removal of the sorbent. Sediment contact with an easily separable model sorbent Tenax beads for 28 days in a slurry phase resulted in 74-98% reduction in polycyclic aromatic hydrocarbon and polychlorinated biphenyl availability compared to the untreated controls. HOC availability in the sorbent-treated sediment slightly increased by sorbent removal and after one month of mixing in a slurry phase because the slowly-desorbing HOC fraction was released and repartitioned back to the sediment, partially replenishing the rapidly-desorbing HOC fraction. However, HOC availability did not further increase during an extended mixing period of 12 months suggesting that the repartitioning process was not an infinite source. HOC availability after the 12-month post-treatment mixing for the sorbent-treated sediment was 53-97% lower than that of the untreated sediment because of the combined effect of HOC mass removal from sediment (with the sorbent) and incomplete recovery of available HOC fraction in the sorbent-treated sediment.


Subject(s)
Environmental Restoration and Remediation/methods , Geologic Sediments/chemistry , Water Pollutants, Chemical/chemistry , Hydrophobic and Hydrophilic Interactions , Polychlorinated Biphenyls/analysis , Polychlorinated Biphenyls/chemistry , Polycyclic Aromatic Hydrocarbons/chemistry , Polymers/chemistry
16.
Environ Sci Technol ; 51(20): 11809-11819, 2017 Oct 17.
Article in English | MEDLINE | ID: mdl-28953372

ABSTRACT

Infrastructure systems that use stormwater and recycled water to augment groundwater recharge through spreading basins represent cost-effective opportunities to diversify urban water supplies. However, technical questions remain about how these types of managed aquifer recharge systems should be designed; furthermore, existing planning tools are insufficient for performing robust design comparisons. Addressing this need, we present a model for identifying the best-case design and operation schedule for systems that deliver recycled water to underutilized stormwater spreading basins. Resulting systems are optimal with respect to life cycle costs and water deliveries. Through a case study of Los Angeles, California, we illustrate how delivering recycled water to spreading basins could be optimally implemented. Results illustrate trade-offs between centralized and decentralized configurations. For example, while a centralized Hyperion system could deliver more recycled water to the Hansen Spreading Grounds, this system incurs approximately twice the conveyance cost of a decentralized Tillman system (mean of 44% vs 22% of unit life cycle costs). Compared to existing methods, our model allows for more comprehensive and precise analyses of cost, water volume, and energy trade-offs among different design scenarios. This model can inform decisions about spreading basin operation policies and the development of new water supplies.


Subject(s)
Groundwater , Recycling , Los Angeles , Water , Water Supply
17.
Water Res ; 121: 109-119, 2017 09 15.
Article in English | MEDLINE | ID: mdl-28525783

ABSTRACT

The aim of this study was to develop a toolset that can be used by site managers to assess and monitor natural attenuation processes in sediments contaminated with legacy hydrophobic organic contaminants. The toolset is composed of sediment traps to measure quality and deposition rate of incoming sediment under different hydrodynamic conditions, sediment cores to show trends in sediment bed concentrations over time, and passive samplers attached to a porewater probe frame to assess the mobility of buried contaminants and possible contaminant flux from sediment. These three tools were used together for the first time to assess the mobility of dichlorodiphenyltrichloroethane (DDT) contaminants in sediment in Pallanza Bay, Lake Maggiore, Italy. Depositing sediment and sediment cores were consistent in showing that DDT-contaminated sediment is undergoing burial by cleaner sediment. Elevated DDT concentrations from historical contamination seemed to be effectively buried and immobilized by ongoing deposition by cleaner sediment, because the positive flux from the elevated DDT concentration in the sediment porewater should not advance towards the sediment surface. The monitoring toolset introduced in this study enabled us to more effectively assess ongoing natural attenuation processes and provide more risk relevant data than traditional methods used in monitored natural recovery projects, such as bulk sediment concentrations from sediment cores. Our field assessment results suggest that incoming sediment from the Toce River have reduced DDT concentrations in the sediment compared to historic levels, and will continue to do so in locations where higher DDT concentrations are found within the bioactive layer.


Subject(s)
Geologic Sediments , Water Pollutants, Chemical , Bays , Environmental Monitoring , Italy , Lakes
18.
Environ Sci Technol ; 51(9): 5156-5164, 2017 May 02.
Article in English | MEDLINE | ID: mdl-28394589

ABSTRACT

Woodchip bioreactors (WBRs) are increasingly being applied to remove nitrate from runoff. In this study, replicate columns with aged woodchips were subjected to a range of measured flow rates and influent nitrate concentrations with an artificial stormwater matrix. Dissolved oxygen (DO), nitrate, and dissolved organic carbon (DOC) were measured along the length of the columns. A multispecies reactive transport model with Michaelis-Menten kinetics was developed to explain the concentration profiles of DO, nitrate, and DOC. Four additional models were developed based on simplifying assumptions, and all five models were tested for their ability to predict nitrate concentrations in the experimental columns. Global sensitivity analysis and constrained optimization determined the set of parameters that minimized the root-mean-squared error (RMSE) between the model and the experimental data. A k-fold validation test revealed no statistical difference in RMSE for predicting nitrate concentrations between a zero-order model and the other multispecies reactive transport models tested. Additionally, the multispecies reactive transport models demonstrated no significant differences in predicting DO and DOC concentrations. These results suggest that denitrification in an aged woodchip bioreactor at constant temperature can effectively be modeled using zero-order kinetics when nitrate concentrations are >2 mg-N L-1. A multispecies model may be used if predicting DOC or DO concentrations is desired.


Subject(s)
Bioreactors , Nitrates , Carbon , Denitrification , Nitrogen Oxides
19.
Environ Sci Process Impacts ; 18(10): 1256-1265, 2016 Oct 12.
Article in English | MEDLINE | ID: mdl-27722395

ABSTRACT

Fipronil is a recalcitrant phenylpyrazole-based pesticide used for flea/tick treatment and termite control that is distributed in urban aquatic environments via stormwater and contributes to stream toxicity. We discovered that fipronil is rapidly metabolized (t1/2 = 4.2 d) by the white rot fungus Trametes versicolor to fipronil sulfone and multiple previously unknown fipronil transformation products, lowering fipronil concentration by 96.5%. Using an LC-QTOF-MS untargeted metabolomics approach, we identified four novel fipronil fungal transformation products: hydroxylated fipronil sulfone, glycosylated fipronil sulfone, and two compounds with unresolved structures. These results are consistent with identified enzymatic detoxification pathways wherein conjugation with sugar moieties follows initial ring functionalization (hydroxylation). The proposed pathway is supported by kinetic evidence of transformation product formation. Fipronil loss by sorption, hydrolysis, and photolysis was negligible. When T. versicolor was exposed to the cytochrome P450 enzyme inhibitor 1-aminobenzotriazole, oxidation of fipronil and production of hydroxylated and glycosylated transformation products significantly decreased (p = 0.038, 0.0037, 0.0023, respectively), indicating that fipronil is metabolized intracellularly by cytochrome P450 enzymes. Elucidating fipronil transformation products is critical because pesticide target specificity can be lost via structural alteration, broadening classes of impacted organisms. Integration of fungi in engineered natural treatment systems could be a viable strategy for pesticide removal from stormwater runoff.


Subject(s)
Insecticides/metabolism , Pyrazoles/metabolism , Trametes/metabolism , Biotransformation , Hydroxylation , Kinetics
20.
Environ Sci Technol ; 50(20): 11025-11033, 2016 10 18.
Article in English | MEDLINE | ID: mdl-27616202

ABSTRACT

Fecal indicator bacteria (FIB) are leading causes of impaired surface waters. Innovative and environmentally appropriate best management practices are needed to reduce FIB concentrations and associated risk. This study examines the ability of the native freshwater mussel Anodonta californiensis and an invasive freshwater clam Corbicula fluminea to reduce concentrations of the FIB Escherichia coli in natural waters. Laboratory batch experiments were used to show bivalve species-specific E. coli removal capabilities and to develop a relationship between bivalve size and clearance rates. A field survey within an impaired coastal river containing both species of bivalves in an agricultural- and grazing-dominated area of the central coast of California showed a significant inverse correlation between E. coli concentration and bivalve density. An in situ field spiking and sampling study showed filtration by freshwater bivalves resulting in 1-1.5 log10 reduction of E. coli over 24 h, and calculated clearance rates ranged from 1.2 to 7.4 L hr-1 bivalve-1. Results of this study show the importance of freshwater bivalves for improving water quality through the removal of E. coli. While both native and invasive bivalves can reduce E. coli levels, the use of native bivalves through integration into best management practices is recommended as a way to improve water quality and protect and encourage re-establishment of native bivalve species that are in decline.


Subject(s)
Escherichia coli , Rivers , Animals , Anodonta , Corbicula , Fresh Water
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